Cyclic c18 and c20 alcohols



United States Patent US. Cl. 260-617 7 Claims ABSTRACT OF THE DISCLOSURE Disubstituted cyclohexane monocarboxylic acids having 18 and 20' carbon atoms are catalytically reduced to the corresponding alcohols. The latter have high molecular weights and low melting points, are not readily subject to oxidative deterioration, and are useful as substitutes for palmityl alcohol and lanolin is cosmetic creams.

A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to novel very low melting, odorless C and C saturated cyclic alcohols (disubstituted cyclohexanes) that exhibit unobvious properties in cosmetic preparations such as body lotions and hand creams.

More specifically, this invention relates to novel liquid alcohols, which are prepared by catalytically reducing the linolenate-derived saturated C cyclic acids of Scholfield et al., JOACS 36: 631 (1959) or the corresponding C ethylene adducts of Beal, US. Pat. No. 3,005,840. We have also discovered that our odorless saturated cyclic alcohols may be advantageously substituted in whole or in part for the distinctly odoriferous palmityl (cetyl) alcohol that is a conventional constituent of cosmetic creams and lotions to provide cosmetics that require little if any masking and to give creams that have an appealingly softer texture and an exceptionally rapid, lanolin-like absorption by the skin. Our cyclic alcohols which are storage stable and not readily subject to oxidative deterioration may also be substituted for lanolin to provide rapidly absorbable cosmetics that are free of lanolins susceptibility to rancidity.

Also, as taught and specifically claimed in application S.N. 350,925 of Theile et al., filed of even date, now US. Pat. No. 3,217,223, when substituted for e.g. spermaceti or other conventional fatty alcohol, fatty acid, of fatty ester in an aluminum oxychloride-containing antiperspirant formulation, our novel cyclic alcohols eliminate the objectionable tacky sensation caused by the aluminum salt astringent.

One object of our invention is the preparation of stable, high molecular weight, very low-melting alcohols having no unsaturation. Another object is the preparation of odorless liquid alcohols that are not only very rapidly absorbed by the skin but which also appear to improve the absorption of the other constituents of a cosmetic emulsion. The subjective and objective comments of a test panel clearly indicated an improved feel and texture and an excellent emollient action.

The above and other objects will be understood more clearly by reference to the following specification and claims.

Our novel C and C saturated cyclic alcohols are isomeric mixtures having the following structures:

Patented May 19, 1970 ice where (x+y)=10 II. CHz(CHz)m-xCH Where (x+y)=8.

The starting materials for our unique alcohols are the known crude or purified isomeric mixtures of the vegetable oil-derived C saturated cyclic acids (vicinally disubstituted cyclohexanes) having the formula i t V CH2(CHZ) XCOOH wherex+y=8 and the corresponding C ethylene adducts formed when ethylene is introduced during the cyclization reaction. In the latter material, however, the ring is substituted predominantly in the 1,4 positions instead of in the above indicated vicinal position, and the saturated cyclic monocarboxylic acid mixture consists predominantly of isomers having the structure where (x+y) 10.

The crude saturated cyclic acid starting materials are mixtures comprising about 40 percent of purifiable cyclic acid monomers along with about 53 percent of byproduct stearic acid and about 7 percent of palmitic acid.

Moreover, since our novel cyclic alcohols are formed by catalytic reduction, it is not necessary to limit the starting materials to the C and C saturated cyclic acids or crudes thereof. Esters of the cyclic acids, and more economically the precursor unsaturated cyclohexadiene and cyclohexene type acids can be directly reduced to the saturated cyclic alcohols, and the same is true of their alkyl, e.g., methyl ester analogs. Furthermore, it is not necessary to isolate the above starting materials from their crudes prior to the catalytic reduction since terminal isolation is practicable. It will be appreciated that when the copper chromite-catalyzed reduction is applied to a crude cyclic acid material, the associated aliphatic acids (stearic, oleic, palmitic, unreacted linoleic, linolenic after incidental reduction of mono, di, and triene unsaturation) are also reduced to the corresponding alcohols so that the final crude is a mixture of the C or the C cyclic alcohol isomers and saturated aliphatic alcohols. Since the byproduct aliphatic alcohol constituents in the crude cyclic alcohol mixtures are rather conventional components of cosmetic formulations, the lower cost of the crude cyclic alcohol products may result in their being preferred by industry over the pure cyclic acid isomeric mixtures.

Examples 1-4 show the preparation of the ester intermediates which are then catalytically reduced to the corresponding saturated alcohols as shown in Examples 5-8. Examples 9 and 10 show the direct reduction of the cyclic acids to the cyclic alcohols. Examples 11-20 are presented to show cosmetic formulations in which our novel cyclic alcohols have been substituted for the conventional cetyl alcohol and/or for lanolin. Table I provides chemical and physical data on our cyclic alcohol products.

EXAMPLE 1 Crude C cyclic acid monomer material (250 g.) prepared by alkali cyclization of linseed oil and comprising 40 percent unsaturated C cyclic acid isomers along with 52 percent C aliphatic acids (stearic, oleic, unreacted isomeric linolenic and linoleic) and 8 percent palmitic acid were refluxed for 2 hours with 200 ml. absolute methanol, 100 ml. dimethoxypropane, and 1 ml. concentrated HCl. The mixed methyl esters (255.6 g.) were recovered and then flash distilled at 0.1 mm. Hg pressure to give 255.3 g. of the mixed ester product.

EXAMPLE 2 Purified hydrogenated i.e., saturated C cyclic acid monomers (183.4 g.) that were freed of dimeric and polymeric material by flash distillation =after acidification of the crude acids and of aliphatic acids by low temperature crystallization from acetone, were refluxed with 500 ml. absolute methanol and 4 ml. concentrated H 80 190.2 g. of essentially pure methyl esters of the saturated C cyclic acid isomers were recovered by flash distillation at a pressure of 0.1 mm. Hg.

EXAMPLE 3 A crude C unsaturated ethylene adduct mixture (501.7 g.) from the cyclization of soybean oil fatty acids in the presence of ethylene, see Friedrich et al., JOACS 39: 420 (1962) was refluxed with 1400 ml. absolute methanol and ml. concentrated H 50 The crude product comprising 46.9 percent by weight of esterified unsaturated C cyclic acid methyl esters was recovered and fiash distilled at 0.1-0.2 mm. pressure (yield 464 g. of the methyl esters of the mixed C cyclic and the aliphatic acids).

EXAMPLE 4 The C ethylene adduct (632 g.) of unsaturated acid product from substantially (96%) pure linoleic acid, see Friedrich et al., JOACS 39, ibid, was refluxed with 1700 ml. absolute methanol and 12.5 ml. concentrated H 50 Flash distillation of the esters gave 582 g. of unsaturated C cyclic acid methyl ester product analyzing 83.6 percent methyl ester of the C unsaturated cyclic acids, 6.8 percent of isomeric methyl linoleate, 3.2 percent of methyl stearate, 4.2 percent of methyl oleate, and 2.2 percent of methyl palmitate.

Substantially identical yields were obtained when the sulfuric acid catalyst was replaced by boron trifluoride etherate or by a hydrogen chloride-dimethoxy propane catalyst system.

EXAMPLE 5 A 500 ml. stainless steel autoclave equipped with a magnetic stirrer, pressurized gas admission means, and

heating mantle was charged with 200 g. of the crude C unsaturated cyclic methyl ester mixture of Example 1 and 20 g. (10% by weight) of a commercial copper chromite catalyst comprising 40 percent CuO, 47 percent Cr O and 10 percent BaO. After flushing, the autoclave was pressurized with hydrogen to 2100 p.s.i. at room temperature and then rapidly heated with stirring to 280 C. At 145 C. and 2,525 p.s.i., a rapid uptake of hydrogen began. During the third (final) hour of reaction at 280 C. the hydrogen uptake was almost negligible. After cooling, the contents were diluted with 200 m acetone and the catalyst removed by filtration on a steamheated funnel. The acetone was stripped off, and the alcohols were flash distilled using a nitrogen sweep at 0.07-0.14 mm. and a steam-heated condenser; 168.2 g. of a distillate fraction boiling at 118168 C. and representing a 98 percent conversion of the esters of both the C cyclic acids and the aliphatic acids to the saturated alcohols was obtained along with 15.7 g. of residue.

EXAMPLE 6 190 g. of the methyl esters of purified saturated C cyclic acid isomers of Example 2 were reduced in the apparatus of Example 5. Since the ring portion of the cyclic acid ester was already saturated, the reaction did not require additional hydrogen for that purpose. Upon stripping the acetone there remained 155 g. of saturated C cyclic alcohol isomers. Distillation gave 1.7 g. of a fraction boiling at 103l29 C./0.15 mmt; 142.9 g. of a fraction boiling lat 129152 C./0.15 mm.; and 6.8 g. of residue. Because the main fraction showed only 69 percent conversion of ester to alcohol (by hydroxyl determination), the alcohols were redistilled in a vacuumjacketed Vigreux column. The first fraction (18.5 g.) boiling at 129 C./0.07 mm. had a refractive index 11 of 1.4638 and by GLC analysis represented a 79 percent conversion of ester to alcohol along with the formation of 21 percent hydrocarbon. The second fraction (64.9 g.) boiling at 129134 C./0.07 mm. and representing a 98.8 percent conversion had a. refractive index of 1.4685. The third fraction (44.8 g.) boiling at 134-138 C./0.07 mm. had a refractive index of 1.4694. Since GLC analysis showed the second and third fractions to be identical, they were combined, n 1.4689.

EXAMPLE 7 450 g. of the mixed methyl esters of the C unsaturated cyclic acid mixture of Example 3 (46.9 percent C cyclic acid methyl esters, 6.6 percent unreacted conjugated methyl linoleate, 26.0 percent methyl oleate, 5.4 percent methyl stearate, and 15.1 percent methyl palmitate) were placed in a 1000 ml. stainless steel autoclave along with 45 g. of copper chromite catalyst and then treated exactly as in Example 5. Distillation of the crude alcohol mixture (414.3 g.) yielded 8 g. of a fraction boiling at 90131 C./0.04 mm.; 379 g. boiling at 131- 180 C./0.04-0.0S mm.; and 32.3 g. residue. The conversion to the saturated alcoho s was 96.5 percent.

EXAMPLE 8 500 g. of the mixed methyl ester product of Example 4 and containing 83.6 percent of the esterified unsaturated C cyclic acids, 6.8 percent unreacted conjugated methyl linoleate, 3.2 percent methyl stearate, 4.2 percent of methyl oleate, and 2.2 percent methyl palmitate were hydrogenated in the presence of 42 g. of copper chromite catalyst exactly as in Example 7. Distillation of the alcohols (441.8 g.) gave 1.8 g. boiling at l30 C./0.1 mm.; 389 g. boiling at -180 C./0.10.2 mm.; and 40.2 g. residue. Conversion of ester to alcohol was 93 percent EXAMPLE 9 A 2 liter autoclave of the type used in Example 5 was charged with 400 g. of crude unsaturated C cyclic acid material obtained by an alkali cyclization of linseed oil. This crude material comprised 37.4 percent C unsaturated cyclic acid monomers and 9.5 percent polymeric residue. After introducing 40 g. of commercial copper chromite catalyst, the autoclave was flushed and pressurized with hydrogen to 2100 p.s.i. at room temperature, followed by a rapid heating to 280 C. A sample taken at 5 hours had an iodine value of 20 and acid value of 10.5; at 9 hours of reduction the respective values were 14 and 6; and at 11 hours they were 14 and less than 1. The crude cyclic alcohols (370 g.) were recovered as described in Example 5, using 400 ml. acetone. To determine whether there was residual unsaturation, 112 g. of the acetone-free crude alcohols were flash distilled, yielding 108.5 g. of a fraction having an iodine value of 6.5 and 2.4 g. of a residue with an iodine value of 49.5. After recombining the distillate fractions and the remaining crude alcohols, 36 g. of fresh catalyst was added to the 360 g. of crude cyclic alcohol mixture, and hydrogenation was resumed for 4 hours at 280 C. Following the recovery of the crude saturated C cyclic alcohols (322.8 g.) having an iodine value of 2.7 and acid value of 0.6, distillation of a 176 g. portion thereof gave 7.5 g. of a fraction boiling at 90-120 C./0.15 mm.; g. of a fraction boiling at 120-160 6 C./ 0.15 mm.; and 12.2 g. of residue. GLC analysis of the Part B: Percent first fraction showed it to consist of 36 percent saturated Cetyl trimethyl ammonium chloride 0.5 C cyclic alcohols, 40.6 percent stearyl alcohol, 14.3 H O 69,5 percent palmityl alcohol, and 9.1 percent hydrocarbon. The main fraction (96 percent conversion of acids to EXAMPLE l3 alcohols) having an acid value of 0.65, iodine value of 5 PartA: 0.48, and melting at 38-46 C. analyzed at 37.8 percent Crude C linseed cyclic (40%) alcohol of Exsaturated C cyclic alcohol isomers, 57.5 percent stearyl ample 5 (in place of cetyl alcohol) 16.0 alcohol, and 4.7 percent palmityl alcohol. Lanolin 16.0 EXAMPLE 1O lsopropylmynstate 16.0

The glass liner of a 300 ml. high pressure rocker auto- Part 3 clave was charged with 63 g. of the pure C unsatu- Tnton X400 Rohm and Haas for rated cyclic acid obtained by the 1-4- addition of ethyloctylphenyl'polyethoxy ethanol cue to 9,11-t,t-octadecadienoic acid and 6.3 g. of copper 2 chromite catalyst. After pressurizing with hydrogen to EXAMPLE 14 2100 psi. at room temperature, the autoclave was heated to 280 C. and the contents reacted for 4% hours. After PartA: cooling and diluting the contents with 200 ml. acetone, Crud? C20 soybeem fychc (475%) am of the catalyst was filtered off. Distillation of the product 20 Penment 7 (Subst for cetyl (50 g.) gave 4 g. of a fraction boiling at 108-l50 lanolin 16.0 C./0.07-0.1 mm., N 1.4650; 34 g. of a fraction boil- Isopropyl myristate 1.54 ing at 150-165" C./0.l-0.2 mm, N 1.4668; and 4 g. Part1} residue. GLC analysis of the main fraction showed only I t 1 h I 1 th th 1 4 extremely faint traces of stearyl alcohol and hydrocar- S006 yp any PO ye oxy 6 am bons H2O 48.0

TABLE I Cyclic, OH, Viscosity, Saturated cyclic alcohols percent percent LV. Acid V. M.P., C. cps, 60 C.

015 linseed-derived monomers (crude) 40 6. 14 0. 7 0. 42-53 11. 65 C18 (purifie 100 6. 2 1.1 0. 45 1 -40 18. 7 C20 soybean monomers (crude) 47. 9 5. 8 1.3 0.56 37-51 14.8 020 (from ethylene adduct of methyl linoleate) 80. 2 5. 4 1. 0 0. 47 23-25 18. 7 C20 from ethylene adduet of pure 9,ll-t,t-octadecadienoie acid 100 5. 5 0.3 O. 99 22-25 28.0

Pour point.

In the following standard hand creams and body lo- EXAMPLE 15 tion formulations shown in Sagerin, Cosmetics, Science Part A: and Technology publlshed 1957 by lnterscience Publ. Crude C li eed cyclic (40%) alc. of Ex. 4 g l i i h l l f bfiu l t g k l fg; 40 (substd. for cetyl alc. and lanolin) 32.0

cyccacoos ave eensus1 e,assown, ce t yl alcohol or for lanolin or both. The emulsions were lsopropyl mynstate u prepared by the conventional procedure of separately Part3: preparing the phases, slowly adding the oil phase (Part 15octylphenyl-polyethoxy ethanol 440 A) at 70-75 C. to the aqueous (external) phase (Part 45 H O 48.01 B) at the same temperature with stirring that was main- EXAMPLE 16 tained until room temperature was reached. The viscosi- Part A. ties of the formulations containing the C cyclic alcohol I materials were generally somewhat lower than in the corcrude lmseed cyFhc (40%) of 5 res onding formulations employing the C cyclic alco- 50 (Subst for lanolm) hols and this difference was greater in the non-ionic Cetyl alcohol formulations. However, the slight differences in viscosity P PYI m-yristate 16.0 did not noticeably afiect the very rapid absorption nor part3: the superior esthetic qualities. Examples 11 and 12 are I500ctylphenyppolyethoxy ethanol 40 cationic, Examples 13-17 are non-ionic, and Examples H20 48 0 18-20 are anionic non-soap formulations. All percentages refer to parts by weight. EXAMPLE 17 EXAMPLE 11 Part Part A: Percent Crude soybean C cycl-ic (47.6%) alcohol of Crude C saturated cycli (40%) alcohol of 7 (Substdfor 131101111) Example S (substituted for cetyl alcohol) 15 y alcohol 16.0 Parafl'in 10 3; Light mineral oil 5 Isooctylphenyl-polyethoxy ethanol 4,0 PartB: H O 48.0

Cetyl trimethyl ammonium chloride 0.5 H20 695 EXAMPLE 18 (LOTION) EXAMPLE 12 Part A1 Part 70 Crude (40%) linseed cyclic (40%) alcohols Crude C cyclic (47.6%) alcohol of Example 5 100 7 (in place of cetyl alcohol) 15 Sodlum cetyl Sulfate .0 Paraflin 10 aric d 8.0 Light mineral oil 5 Stearyl alcohol 3.0

7 Part B: Percent Glycerol 8.0 Sodium cetyl sulfate 1.0 H 0 68.0

EXAMPLE 19 Part A:

Crude soybean C cyclic (47.6%) alcohols of Ex. 7 10.0 Sodium cetyl sulfate 2.0 Stearic acid 8.0 Stearic alcohol 3.0

Part B:

Glycerol 8.0 Sodium cetyl sulfate 1.0 H 0 68.0

EXAMPLE 20 Part A:

Purified C satd. cyclic alcohols of Ex. 6 10.0 Sodium cetyl sulfate 2.0 Stearic acid 8.0 Stearyl alcohol 3.0 Part B:

Glycerol 8.0 Sodium cetyl sulfate 1.0 H 0 68.0

It is clear that those skilled in the cosmetic art can make many obvious adjustments and modifications based on the present disclosure without departing from the spirit of our invention.

We claim:

1. A product obtained by heating, at l45280 C. under 2,100 to 2,525 p.s.i. hydrogen pressure in the presence of 10 percent copper chromite catalyst containing 10 percent barium oxide, a starting material selected from the group consisting of methyl esters of crude C unsaturated cyclic acids prepared by alkali cyclization of linseed oil, methyl esters of purified saturated C cyclic acids prepared by alkali cyclization of linseed oil, methyl esters of C cyclic acids prepared by alkali cyclization of soybean oil fatty acids in the presence of ethylene,

methyl esters of C cyclic acids prepared by alkali cyclization of linoleic acid in the presence of ethylene, C unsaturated cyclic acids prepared by alkali cyclization of linseed oil, and pure C unsaturated cyclic acids prepared by the 1, 4- addition of ethylene to 9,l1-t,t-octadecadienoic acid.

2. The product by the process of claim 1 in which the starting material is the methyl esters of crude C unsaturated cyclic acids prepared by alkali cyclization of linseed oil.

3. The product by the process of claim 1 in which the starting material is the methyl esters of purified saturated C cyclic acids prepared by alkali cyclization of linseed oil.

4. The product by the process of claim 1 in which the starting material is C unsaturated cyclic acids prepared by alkali cyclization of linseed oil.

5. The product by the process of claim 1 in which the starting material is the methyl esters of C cyclic acids prepared by alkali cyclization of soybean oil fatty acids in the presence of ethylene.

6. The product by the process of claim 1 in which the starting material is the methyl esters of C cyclic acids prepared by the alkali cyclization of linoleic acid in the presence of ethylene.

7. The product by the process of claim 1 in which the starting material is the pure C unsaturated cyclic acids prepared by the 1,4-addition of ethylene to 9,11-t,t-0ctadecadienoic acid.

References Cited UNITED STATES PATENTS 2,347,562 4/1944 Johnston 260617 2,415,335 2/1947 Bruson et al. 260617 2,828,340 3/1958 Dickenson et al. 260-617 BERNARD HELFIN, Primary Examiner J. E. EVANS, Assistant Examiner U.S. Cl. X.R. 260-468, 638 

